US7351759B2 - Rubber composition for a tire comprising a coupling agent having a polythiosulfenamide function - Google Patents

Rubber composition for a tire comprising a coupling agent having a polythiosulfenamide function Download PDF

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US7351759B2
US7351759B2 US10/733,613 US73361303A US7351759B2 US 7351759 B2 US7351759 B2 US 7351759B2 US 73361303 A US73361303 A US 73361303A US 7351759 B2 US7351759 B2 US 7351759B2
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tire according
group
tire
tread
formula
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US20040181000A1 (en
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José-Carlos Araujo-Da-Silva
Christiane Blanchard
Gérard Mignani
Salvatore Pagano
Jean-Claude Tardivat
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Compagnie Generale des Etablissements Michelin SCA
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Michelin Recherche et Technique SA Switzerland
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/548—Silicon-containing compounds containing sulfur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S152/00—Resilient tires and wheels
    • Y10S152/905—Tread composition

Definitions

  • the present invention relates to compositions of diene elastomers reinforced with a white or inorganic filler, intended particularly for the manufacture of tires or of semi-finished products for tires, in particular of treads for these tires.
  • Such rubber compositions comprising reinforcing inorganic fillers for example of the silica or alumina type have for example been described in the patents or patent applications EP 501 227 or U.S. Pat. No. 5,227,425, EP 735 088 or U.S. Pat. No. 5,852,099, EP 810 258 or U.S. Pat. No. 5,900,449, EP 881 252, WO99/02590, WO99/06480, WO00/05300, WO00/05301 and WO02/10269.
  • a coupling agent also referred to as bonding agent, the function of which is to provide the bond between the surface of the particles of inorganic filler and the elastomer, while facilitating the dispersion of this inorganic filler within the elastomeric matrix.
  • coupling agent is understood in known manner to mean a compound capable of establishing a sufficient chemical and/or physical connection between the inorganic filler and the diene elastomer; such a coupling agent, which is at least bifunctional, has, for example, the simplified general formula “Y-T-X”, in which:
  • the coupling agents must particularly not be confused with simple agents for covering the inorganic filler which, in known manner, may comprise the Y function which is active with respect to the inorganic filler but are devoid of the X function which is active with respect to the diene elastomer.
  • Coupling agents in particular (silica/diene elastomer) coupling agents, have been described in a large number of documents, the best known being bifunctional organosilanes bearing three organoxysilyl (in particular alkoxysilyl) functions as “Y” function and, as “X” function, at least one function capable of reacting with the diene elastomer, such as, in particular, a sulfurised functional group (i.e. comprising sulfur).
  • TESPT bis-3-triethoxysilylpropyl tetrasulfide
  • TESPD bis 3-triethoxysilylpropyl disulfide
  • polysulfurised alkoxysilanes are generally considered as the products providing, for vulcanized rubber compositions comprising a reinforcing inorganic filler, in particular silica, the best compromise in terms of resistance to scorching, ease of processing and reinforcing ability.
  • TESPT polysulfurised alkoxysilanes
  • they are the coupling agents which are most used today in rubber compositions for tires, even if they have the known drawbacks (see for example patents U.S. Pat. No. 5,652,310, U.S. Pat. No. 5,684,171, U.S. Pat. No. 5,684,172) of being relatively costly and, what is more, of needing to be used most frequently in relatively large quantities.
  • These coupling agents are organosilicon compounds which have the essential characteristic of bearing, as X function, a specific polythiosulfenamide functional group. Furthermore, they do not have the aforementioned scorching and processing problems which are linked to excessive viscosity of the rubber compositions in the uncured state, which disadvantages are found in particular with mercaptosilanes.
  • a first subject of the invention relates to an elastomeric composition usable for the manufacture of tires, comprising at least, as base constituents, (i) a diene elastomer, (ii) an inorganic filler as reinforcing filler and (iii), as (inorganic filler/diene elastomer) coupling agent, a polysilylated organosilicon compound which is at least bifunctional and can be grafted onto the elastomer by means of a sulfur group having a polythiosulfenamide function, of formula: ⁇ Si-A-S x —NR 1 R 2 (I) in which:
  • Another subject of the invention is the use of a rubber composition according to the invention for the manufacture of tires or for the manufacture of semi-finished products intended for such tires, these semi-finished products being selected in particular from among the group comprising treads, underlayers intended for example to be positioned beneath these treads, crown reinforcement plies, sidewalls, carcass reinforcement plies, beads, protectors, inner tubes and airtight internal rubbers for tubeless tires.
  • a further subject of the invention is these tires and these semi-finished products themselves, when they comprise an elastomeric composition according to the invention, these tires being intended to be fitted on passenger vehicles, 4 ⁇ 4 vehicles (having 4 driving wheels), SUVs (“Sport Utility Vehicles”), two-wheeled vehicles (in particular bicycles or motorcycles), and also industrial vehicles selected from among vans, “heavy vehicles”—i.e. subway trains, buses, road transport machinery (lorries, tractors, trailers), off-road vehicles—, agricultural machinery or construction machinery, aircraft and other transport or handling vehicles.
  • passenger vehicles 4 ⁇ 4 vehicles (having 4 driving wheels), SUVs (“Sport Utility Vehicles”), two-wheeled vehicles (in particular bicycles or motorcycles), and also industrial vehicles selected from among vans, “heavy vehicles”—i.e. subway trains, buses, road transport machinery (lorries, tractors, trailers), off-road vehicles—, agricultural machinery or construction machinery, aircraft and other transport or handling vehicles.
  • SUVs Sport Utility Vehicles
  • two-wheeled vehicles in particular bicycles or
  • the invention relates in particular to treads for tires, these treads being able to be used in the manufacture of new tires or for recapping worn tires; owing to the compositions of the invention, these treads have all of the following: low rolling resistance, very good grip and high wear resistance.
  • the invention also relates to a process for the preparation of a rubber composition usable for the manufacture of tires, such a process comprising the following steps:
  • a further subject of the invention is the use as (inorganic filler/diene elastomer) coupling agent, in a composition based on diene elastomer reinforced by an inorganic filler intended for the manufacture of tires, of an organosilicon compound, which is at least bifunctional and can be grafted on to the elastomer by means of a sulfur group, having a polythiosulfenamide function, of the aforementioned formula (I).
  • a subject of the invention is a process for coupling an inorganic filler and a diene elastomer, in an elastomeric composition usable for the manufacture of tires, such process comprising the following steps:
  • FIG. 1 rheograms (curing curves) recorded for rubber compositions whether or not in accordance with the invention
  • FIG. 2 curves of variation in modulus as a function of the elongation for these rubber compositions.
  • the rubber compositions are characterized before and after curing, as indicated below.
  • the Mooney plasticity is measured in accordance with the following principle: the uncured composition (i.e. before curing) is molded in a cylindrical enclosure heated to 100° C. After one minute's preheating, the rotor turns within the test piece at 2 rpm, and the torque used for maintaining this movement is measured after four minutes of rotation.
  • the measurements are effected at 130° C., in accordance with French Standard NF T 43-005 (1991).
  • the evolution of the consistometric index as a function of time makes it possible to determine the scorching time for the rubber compositions, assessed in accordance with the above standard by the parameter T5 (case of a large rotor), expressed in minutes, and defined as being the time necessary to obtain an increase in the consistometric index (expressed in MU) of 5 units above the minimum value measured for this index.
  • the measurements are effected at 150° C. with an oscillating-chamber rheometer, in accordance with DIN Standard 53529—part 3 (June 1983).
  • the evolution of the rheometric torque as a function of time describes the evolution of the stiffening of the composition following the vulcanization reaction.
  • the measurements are processed in accordance with DIN Standard 53529—part 2 (March 1983): t i is the induction period, that is to say, the time necessary for the start of the vulcanization reaction; t ⁇ (for example t 90 or t 99 ) is the time necessary to achieve a conversion of ⁇ %, that is to say ⁇ % (for example 90% or 99%, respectively) of the deviation between the minimum and maximum torques.
  • the conversion rate constant K (expressed in min ⁇ 1 ) of order 1, calculated between 30% and 80% conversion, is also measured, which makes it possible to assess the vulcanization kinetics.
  • Processing the tensile data recorded also makes it possible to trace the curve of the modulus as a function of the elongation (see FIG. 2 ), the modulus used here being the true secant modulus measured in a first elongation, calculated reduced to the real cross-section of the test sample and not to the initial section, as previously for the nominal moduli.
  • the rubber compositions according to the invention are based on at least each of the following constituents: (i) a (at least one) diene elastomer, (ii) a (at least one) inorganic filler as reinforcing filler, and (iii) a (at least one) specific organosilicon compound as (inorganic filler/diene elastomer) coupling agent.
  • composition “based on” is to be understood to mean a composition comprising the mix and/or the product of reaction in situ of the various constituents used, some of these base constituents being liable to, or intended to, react together, at least in part, during the different phases of manufacture of the composition, in particular during the vulcanization thereof.
  • “Diene” elastomer or rubber is understood to mean, in known manner, an elastomer resulting at least in part (i.e. a homopolymer or a copolymer) from diene monomers (monomers bearing two double carbon-carbon bonds, whether conjugated or not).
  • essentially unsaturated diene elastomer is understood here to mean a diene elastomer resulting at least in part from conjugated diene monomers, having a content of members or units of diene origin (conjugated dienes) which is greater than 15% (mol %).
  • diene elastomers such as butyl rubbers or copolymers of dienes and of alpha-olefins of the EPDM type do not fall within the preceding definition, and may in particular be described as “essentially saturated” diene elastomers (low or very low content of units of diene origin which is always less than 15%).
  • “highly unsaturated” diene elastomer is understood to mean in particular a diene elastomer having a content of units of diene origin (conjugated dienes) which is greater than 50%.
  • Suitable conjugated dienes are, in particular; 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di(C 1 -C 5 alkyl)-1,3-butadienes such as, for instance, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl-1,3-butadiene, an aryl-1,3-butadiene, 1,3-pentadiene and 2,4-hexadiene.
  • Suitable vinyl-aromatic compounds are, for example, styrene, ortho-, meta- and para-methylstyrene, the commercial mixture “vinyltoluene”, para-tertbutylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene and vinylnaphthalene.
  • the copolymers may contain between 99% and 20% by weight of diene units and between 1% and 80% by weight of vinyl aromatic units.
  • the elastomers may have any microstructure, which is a function of the polymerization conditions used, in particular of the presence or absence of a modifying and/or randomizing agent and the quantities of modifying and/or randomizing agent used.
  • the elastomers may for example be block, statistical, sequential or microsequential elastomers, and may be prepared in dispersion or in solution; they may be coupled and/or starred or alternatively functionalized with a coupling and/or starring or functionalizing agent.
  • polybutadienes and in particular those having a content of 1,2-units between 4% and 80%, or those having a content of cis-1,4 of more than 80%, polyisoprenes, butadiene-styrene copolymers, and in particular those having a styrene content of between 5% and 50% by weight and, more particularly, between 20% and 40%, a content of 1,2-bonds of the butadiene fraction of between 4% and 65%, and a content of trans-1,4 bonds of between 20% and 80%, butadiene-isoprene copolymers and in particular those having an isoprene content of between 5% and 90% by weight and a glass transition temperature (Tg, measured in accordance with ASTM Standard D3418-82) of from ⁇ 40° C.
  • Tg glass transition temperature
  • isoprene-styrene copolymers and in particular those having a styrene content of between 5% and 50% by weight and a Tg of between ⁇ 25° C. and ⁇ 50° C.
  • butadiene-styrene-isoprene copolymers those which are suitable are in particular those having a styrene content of between 5% and 50% by weight and, more particularly, between 10% and 40%, an isoprene content of between 15% and 60% by weight, and more particularly between 20% and 50%, a butadiene content of between 5% and 50% by weight, and more particularly between 20% and 40%, a content of 1,2-units of the butadiene fraction of between 4% and 85%, a content of trans-1,4 units of the butadiene fraction of between 6% and 80%, a content of 1,2- plus 3,4-units of the isoprene fraction of between 5% and 70%, and a content of trans-1,4 units of the isoprene fraction of between 10% and 50%, and more generally any butadiene-styrene-isoprene copolymer having a Tg of between ⁇ 20° C. and ⁇ 70° C.
  • the diene elastomer of the composition according to the invention is selected from the group of highly unsaturated diene elastomers which consists of polybutadienes (BR), polyisoprenes (IR), natural rubber (NR), butadiene copolymers, isoprene copolymers and mixtures of these elastomers.
  • Such copolymers are more preferably selected from the group which consists of butadiene-styrene copolymers (SBR), butadiene-isoprene copolymers (BIR), isoprene-styrene copolymers (SIR) and isoprene-butadiene-styrene copolymers (SBIR).
  • SBR butadiene-styrene copolymers
  • BIR butadiene-isoprene copolymers
  • SIR isoprene-styrene copolymers
  • SBIR isoprene-butadiene-styrene copolymers
  • composition according to the invention is particularly intended for a tread for a tire, be it a new or a used tire (case of recapping).
  • the diene elastomer is for example an SBR, be it an SBR prepared in emulsion (“ESBR”) or an SBR prepared in solution (“SSBR”), or an SBR/BR, SBR/NR (or SBR/IR), or alternatively BR/NR (or BR/IR), blend (mixture).
  • SBR elastomer in particular an SBR having a styrene content of between 20% and 30% by weight, a content of vinyl bonds of the butadiene fraction of between 15% and 65%, a content of trans-1,4 bonds of between 15% and 75%, and a Tg of between ⁇ 20° C. and ⁇ 55° C. is used.
  • Such an SBR copolymer, preferably prepared in solution (SSBR) is possibly used in a mixture with a polybutadiene (BR) having preferably more than 90% cis-1,4 bonds.
  • the diene elastomer is in particular an isoprene elastomer; isoprene elastomer” is understood to mean, in known manner, an isoprene homopolymer or copolymer, in other words a diene elastomer selected from the group consisting of natural rubber (NR), synthetic polyisoprenes (IR), the various isoprene copolymers and mixtures of these elastomers.
  • NR natural rubber
  • IR synthetic polyisoprenes
  • isoprene copolymers are examples of isobutene-isoprene copolymers (butyl rubber—IIR), isoprene-styrene copolymers (SIR), isoprene-butadiene copolymers (BIR) or isoprene-butadiene-styrene copolymers (SBIR).
  • This isoprene elastomer is preferably natural rubber or a synthetic cis-1,4 polyisoprene; of these synthetic polyisoprenes, preferably polyisoprenes having a content (mole %) of cis-1,4 bonds greater than 90%, more preferably still greater than 98%, are used.
  • the diene elastomer may also be constituted, in its entirety or in part, of another highly unsaturated elastomer such as, for example, an SBR elastomer.
  • the composition according to the invention may contain at least one essentially saturated diene elastomer, in particular at least one EPDM copolymer, whether this copolymer be used or not used, for example, in a mixture with one or more of the highly unsaturated diene elastomers mentioned above.
  • compositions of the invention may contain a single diene elastomer or a mixture of several diene elastomers, the diene elastomer or elastomers possibly being used in association with any type of synthetic elastomer other than a diene elastomer, or even with polymers other than elastomers, for example thermoplastic polymers.
  • the white or inorganic filler used as reinforcing filler may constitute all or only part of the total reinforcing filler, in this latter case associated, for example, with carbon black.
  • the reinforcing inorganic filler constitutes the majority, i.e. more than 50% by weight, of the total reinforcing filler, more preferably more than 80% by weight of this total reinforcing filler.
  • “reinforcing inorganic filler”, in known manner, is understood to mean an inorganic or mineral filler, whatever its color and its origin (natural or synthetic), also referred to as “white” filler or sometimes “clear” filler in contrast to carbon black, this inorganic filler being capable, on its own, without any other means than an intermediate coupling agent, of reinforcing a rubber composition intended for the manufacture of tires, in other words which is capable of replacing a conventional tire-grade carbon black filler in its reinforcement function.
  • the reinforcing inorganic filler is a mineral filler of the type silica (SiO 2 ) or alumina (Al 2 O 3 ), or a mixture of these two fillers.
  • the silica used may be any reinforcing silica known to the person skilled in the art, in particular any precipitated or fumed silica having a BET surface area and a specific CTAB surface area both of which are less than 450 m 2 /g, preferably from 30 to 400 m 2 /g.
  • Highly dispersible precipitated silicas referred to as “HDS”) are preferred, in particular when the invention is used for the manufacture of tires having a low rolling resistance; “highly dispersible silica” is understood in known manner to mean any silica having a substantial ability to disagglomerate and to disperse in an elastomeric matrix, which can be observed in known manner by electron or optical microscopy on thin sections.
  • silica Perkasil KS 430 from Akzo
  • the silica BV3380 from Degussa
  • the silicas Zeosil 1165 MP and 1115 MP from Rhodia
  • the silica Hi-Sil 2000 from PPG the silicas Zeopol 8741 or 8745 from Huber
  • treated precipitated silicas such as, for example, the aluminium-“doped” silicas described in application EP-A-0 735 088.
  • the reinforcing alumina preferably used is a highly dispersible alumina having a BET surface area from 30 to 400 m 2 /g, more preferably between 60 and 250 m 2 /g, and an average particle size at most equal to 500 nm, more preferably at most equal to 200 nm, as described in the aforementioned application EP-A-0 810 258.
  • Non-limitative examples of such reinforcing aluminas are in particular the aluminas “Baikalox” “A125”, “CR125” and “D65CR” from Ba ⁇ kowski.
  • reinforcing inorganic filler is also understood to mean mixtures of different reinforcing inorganic fillers, in particular of highly dispersible silicas and/or aluminas such as described above.
  • the reinforcing inorganic filler used in particular if it is silica, preferably has a BET surface area of between 60 and 250 m 2 /g, more preferably between 80 and 200 m 2 /g.
  • the reinforcing inorganic filler may also be used in a blend (mixture) with carbon black.
  • Suitable carbon blacks are all the carbon blacks, in particular the blacks of the type HAF, ISAF and SAF, which are conventionally used in tires, and particularly in treads for tires.
  • the amount of carbon black present in the total reinforcing filler may vary within wide limits, this amount of carbon black preferably being less than the amount of reinforcing inorganic filler present in the rubber composition.
  • compositions according to the invention in particular in the treads incorporating such compositions, it is preferred to use, in a small proportion, a carbon black in association with the reinforcing inorganic filler, in a preferred amount of between 2 and 20 phr, more preferably within a range from 5 to 15 phr.
  • a carbon black in association with the reinforcing inorganic filler, in a preferred amount of between 2 and 20 phr, more preferably within a range from 5 to 15 phr.
  • the coloring properties black pigmentation agent
  • anti-UV properties of the carbon blacks without furthermore adversely affecting the typical performance provided by the reinforcing inorganic filler, namely low hysteresis (reduced rolling resistance) and high adhesion on wet, snow-covered or icy ground.
  • the amount of total reinforcing filler is between 10 and 200 phr, more preferably between 20 and 150 phr, the optimum differing according to the intended applications, because the level of reinforcement expected of a bicycle tire, for example, is in known manner distinctly lower than that required for a tire liable to travel at a sustained high speed, for example a motorcycle tire, a passenger-vehicle tire or a tire for a utility vehicle such as a heavy vehicle.
  • the quantity of reinforcing inorganic filler is preferably between 30 and 140 phr, more preferably within a range from 50 to 120 phr.
  • the BET specific surface area is determined in known manner, in accordance with the method of Brunauer, Emmett and Teller described in “ The Journal of the American Chemical Society ”, vol. 60, page 309, February 1938, and corresponding to French Standard NF T 45-007 (November 1987); the CTAB specific surface area is the external surface area determined in accordance with the same Standard NF T 45-007.
  • an (inorganic filler/diene elastomer) coupling agent bears at least two functions, referred to here as “Y” and “X”, which enable it to be grafted, on one hand to the reinforcing inorganic filler by means of the Y function, for example a hydroxyl group or a hydrolyzable group, and on the other hand to the diene elastomer by means of the X function, for example a sulfur function.
  • polysilylated organosilicon compound used as coupling agent in the compositions according to the invention can be grafted onto the elastomer by means of a sulfur group having a polythiosulfenamide function, of formula: ⁇ Si-A-S x —NR 1 R 2 , (I) in which:
  • organosilicon (or “organosilicic”) compound is to be understood to mean, by definition, an organic compound comprising at least one carbon-silicon bond. It will be understood that the compound of formula (I) above, which bears at least two different silicon atoms (at least one bonded to the group A, at least one other bonded to the group B), therefore falls within the category of organosilicon compounds of the polysilylated type. It will furthermore be noted that when R 1 is identical (in its general formula) to R 2 , then the compound of formula (I) bears at least three different silicon atoms.
  • the number x is then an integer which is equal to 2, 3 or 4, preferably equal to 2 or 3.
  • this number may be an average fractional number when the synthesis path gives rise to a mixture of polysulfurized groups each having a different number of sulfur atoms.
  • the polythiosulfenamide group which is synthesized is in fact formed of a distribution of polysulfides, from the disulfide S 2 to heavier polysulfides, centered on an average value (in mole) of the “x”s (fractional number) of between 2 and 4, more preferably of between 2 and 3.
  • the divalent group A is preferably selected from among aliphatic hydrocarbon groups, whether saturated or unsaturated, carbocyclic groups, whether saturated, unsaturated or/and aromatic, monocyclic or polycyclic, and groups having an aliphatic hydrocarbon portion, whether saturated or unsaturated and a carbocyclic portion such as defined above.
  • This bond group A preferably comprises from 1 to 18 carbon atoms, and represents more preferably an alkylene chain, a saturated cycloalkylene group, an arylene group, or a divalent group consisting of a combination of at least two of these groups.
  • the monovalent hydrocarbon group represented by R1 may be aliphatic, straight-chain or branched, or carbocyclic, in particular aromatic; it may be substituted or non-substituted, saturated or unsaturated. In the case of an aliphatic hydrocarbon group, this comprises in particular from 1 to 25 carbon atoms, more preferably from 1 to 12 carbon atoms.
  • alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert. butyl, pentyl, isopentyl, neopentyl, 2-methylbutyl, 1-ethylpropyl, hexyl, isohexyl, neohexyl, 1-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 1,3-dimethylbutyl, 2-ethylbutyl, 1-methyl-1-ethylpropyl, heptyl, 1-methylhexyl, 1-propylbutyl, 4,4-dimethylpentyl, octyl, 1-methylheptyl, 2-ethylhexyl, 5,5-dimethylhexyl, nonyl, decyl, 1-methylnon
  • the unsaturated aliphatic hydrocarbon groups which are usable comprise one or more unsaturated sites, preferably one, two or three unsaturated sites of ethylenic type (double bond) or/and acetylenic type (triple bond).
  • unsaturated aliphatic hydrocarbon groups comprise one or more unsaturated sites, preferably one, two or three unsaturated sites of ethylenic type (double bond) or/and acetylenic type (triple bond).
  • Examples are the alkenyl or alkynyl groups deriving from the alkyl groups defined above by elimination of two hydrogen atoms, or more.
  • the unsaturated aliphatic hydrocarbon groups comprise a single unsaturated site.
  • Carbocyclic radical is understood to mean a monocyclic or polycyclic radical, possibly substituted, preferably a C 3 -C 50 radical.
  • it is a C 3 -C 18 radical which is preferably mono-, bi- or tricyclic.
  • the carbocyclic radical comprises more than one cyclic core (as is the case with polycyclic carbocycles)
  • the cyclic cores are condensed two by two. Two condensed cores may be ortho-condensed or peri-condensed.
  • the carbocyclic radical may, unless indicated otherwise, comprise a saturated portion and/or an aromatic portion and/or an unsaturated portion.
  • saturated carbocyclic radicals are cycloalkyl groups.
  • the cycloalkyl groups are C 3 -C 18 , better still C 5 -C 10 , groups. Mention may be made in particular of the radicals cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl or norbornyl.
  • the unsaturated carbocycle or any unsaturated portion of carbocyclic type has one or more ethylenically unsaturated sites, preferably one, two or three. It advantageously comprises from 6 to 50 carbon atoms, better still from 6 to 20, for example from 6 to 18 carbon atoms.
  • Examples of unsaturated carbocycles are C 6 -C 10 cycloalkenyl groups.
  • Examples of aromatic carbocyclic radicals are C 6 -C 18 aryl groups and in particular phenyl, naphthyl, anthryl and phenanthryl.
  • a group having both an aliphatic hydrocarbon portion and a carbocyclic portion as defined above is, for example, an arylalkyl group such as benzyl, or an alkylaryl group such as tolyl.
  • the substituents of the aliphatic hydrocarbon groups or portions and of the carbocyclic groups or portions are, for example, alkoxyl groups in which the alkyl portion is preferably such as defined above.
  • R 1 preferably comprises from 1 to 25 carbon atoms.
  • R 1 is selected from the group consisting of hydrogen, C 1 -C 8 alkyls, whether straight-chain or branched, C 5 -C 10 cycloalkyls, C 6 -C 18 aryls, (C 6 -C 18 )aryl-(C 1 -C 8 )alkyls and R 2 .
  • R 1 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, hexyl, benzyl, cyclohexyl, phenyl, benzyl and R 2 .
  • the divalent bond groups A and B which may be identical or different, preferably comprising from 1 to 18 carbon atoms, are more preferably selected from among C 1 -C 18 alkylenes (hereafter referred to as “Z”), and C 6 -C 12 arylenes; they may be substituted or interrupted by one or more heteroatoms, selected in particular from among S, O and N.
  • Z more preferably represents a C 1 -C 4 alkylene chain, in particular methylene, ethylene or propylene, more preferably still propylene.
  • R 2 advantageously represents the grouping: —B—SiR 3 (3-a) (OR 4 ) a , in which:
  • the radicals R 3 and R 4 which may be identical or different, are hydrocarbon groups selected in particular from among aliphatic hydrocarbon groups, whether saturated or unsaturated, carbocyclic groups, whether saturated, unsaturated or/and aromatic, monocyclic or polycyclic, and groups having an aliphatic hydrocarbon portion, whether saturated or unsaturated, and a carbocyclic portion such as defined above, preferably comprising from 1 to 18 carbon atoms, these different groups possibly being substituted or not substituted.
  • R 3 which may be identical or different if they are several in number, preferably represent an alkyl, a cycloalkyl or an aryl. They are more preferably selected from among the group consisting of C 1 -C 8 alkyls, C 5 -C 10 cycloalkyls (in particular cyclohexyl) and phenyl. More preferably still, R 3 is selected from the group consisting of C 1 -C 6 alkyls (in particular methyl, ethyl, propyl and isopropyl).
  • the radicals R 4 which may be identical or different if they are several in number, preferably represent an alkyl, a cycloalkyl, an acyl or an aryl. They are more preferably selected from among the group consisting of C 1 -C 8 alkyls, possibly halogenated and/or possibly substituted by one or more (C 2 -C 8 ) alkoxys; C 2 -C 9 acyls, possibly halogenated and/or possibly substituted by one or more (C 2 -C 8 ) alkoxys; C 5 -C 10 cycloalkyls and C 6 -C 18 aryls.
  • R 4 is selected from the group consisting of C 1 -C 8 alkyls (in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, ⁇ -chloropropyl, ⁇ -chloroethyl), possibly substituted by one or more (C 2 -C 8 ) alkoxys (in particular methoxy, ethoxy, propoxy, isopropoxy); C 5 -C 10 cycloalkyls and phenyl.
  • C 1 -C 8 alkyls in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, ⁇ -chloropropyl, ⁇ -chloroethyl
  • C 2 -C 8 alkoxys in particular methoxy, ethoxy, propoxy, isopropoxy
  • C 5 -C 10 cycloalkyls and phenyl is selected from the group consisting of C
  • R 3 and R 4 which may be identical or different, are both selected (if a ⁇ 3) from among C 1 -C 4 alkyls, in particular from among methyl and ethyl.
  • this organosilicon compound is preferably a silane compound bearing as Y function one or more (maximum of 3) (OR) groups fixed to a silicon atom, R representing hydrogen or a monovalent hydrocarbon group, whether straight-chain or branched (in particular alkyl).
  • organosilicon compound particularly suitable for the invention a polysilylated polythiosulfenamide silane of the general formula: (R 6 O) b R 5 (3-b) Si-A-S x —NR 1 —B—SiR 3 (3-a) (OR 4 ) a , (IV) in which:
  • R 5 , R 6 and b have the general preferred meanings given above, respectively, for R 3 , R 4 and a.
  • R 5 is more preferably selected from among the group consisting of C 1 -C 8 alkyls, C 5 -C 10 cycloalkyls and phenyl; more preferably, R 6 is selected from the group consisting of C 1 -C 6 alkyls, C 2 -C 6 alkoxyalkyls, C 5 -C 8 cycloalkyls and phenyl.
  • R 5 and R 6 which may be identical or different, are selected from among C 1 -C 6 alkyls, more preferably still from among C 1 -C 4 alkyls.
  • an organosilicon compound in accordance with this formula (IV) comprises a first “Y” function [symbolized by the 1 to 3 (OR 6 ) b group(s) fixed to the first silicon atom] joined, by means of the bond group A, to the polythiosulfenamide functional group of formula (I) [“X” function symbolized by —S x —N R 1 R 2 ], the latter having the advantageous additional characteristic of comprising at least one second “Y” function [symbolized by the 1 to 3 (OR 4 ) a group(s) joined to the second silicon atom].
  • Z more preferably represents a C 1 -C 4 alkylene chain, in particular methylene, ethylene or propylene, more preferably still propylene; the radicals R 3 , R 4 , R 5 and R 6 , which may be identical or different, more preferably represent a C 1 -C 3 alkyl, in particular methyl or ethyl.
  • organosilicon compounds of formula (V) mention will be made more particularly of those for which R 1 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, hexyl, benzyl, cyclohexyl and phenyl, such as, for example:
  • R 1 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, hexyl, benzyl, cyclohexyl and phenyl;
  • Z represents a C 1 -C 4 alkylene chain, more preferably propylene;
  • the radicals R 3 and R 4 which may be identical or different if R 3 is present (a ⁇ 3), represent more particularly still a C 1 -C 3 alkyl, in particular methyl or ethyl;
  • x is more preferably equal to 2.
  • the polyfunctional coupling agents above which bear a polythiosulfenamide group, have exhibited very good reactivity with respect to the diene elastomers used in rubber compositions for tires, and have proved sufficiently effective on their own for coupling such elastomers and a reinforcing inorganic filler such as silica. Without this being limitative, they may advantageously constitute the sole coupling agent present in the rubber compositions of the invention.
  • the quantity of coupling agent used in the compositions according to the invention lies between 10 ⁇ 7 and 10 ⁇ 5 moles per m 2 of reinforcing inorganic filler. More preferably still, the amount of coupling agent lies between 5 ⁇ 10 ⁇ 7 and 5 ⁇ 10 ⁇ 6 moles per meter squared of total inorganic filler.
  • the content of coupling agent will be preferably greater than 1 phr, more preferably between 2 and 20 phr. Below the minimum amounts indicated, the effect risks being inadequate, whereas beyond the maximum amount advocated generally no further improvement in the coupling is observed, while the costs of the composition increase; for these various reasons, this content of coupling agent is more preferably still between 3 and 12 phr.
  • the coupling agent in a preferred amount representing between 0.5% and 20% by weight relative to the quantity of reinforcing inorganic filler; amounts less than 15%, in particular less than 10%, are more particularly preferred.
  • organosilicon compound previously described could be grafted beforehand (via the “Y” function) onto the reinforcing inorganic filler, the thus “precoupled” filler then being able to be later bonded to the diene elastomer by means of the free “X” function.
  • organosilicon compounds such as described previously may be prepared in accordance with the preferred synthesis paths indicated hereafter (methods referred to as A, B or C).
  • a disulfide halide of formula: (R 6 O) b R 5 (3-b) Si-A-S—S-Hal (VIII) in which A, R 5 , R 6 and b are as defined above and Hal
  • Appropriate bases are, for example, N-methylmorpholine, triethylamine, tributylamine, diisopropylethylamine, dicyclohexylamine, N-methylpiperidine, pyridine, 4-(1-pyrrolidinyl)pyridine, picoline, 4-(N,N-dimethylamino)pyridine, 2,6-di-tert.
  • the reaction is preferably carried out in a polar aprotic solvent such as an ether and, for example, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane or diethyleneglycol dimethyl ether. Diethyl ether is preferred.
  • the reaction temperature is a function of the reactivity of the molecules present and the force of the base used. This temperature generally varies between ⁇ 78° C. and ambient temperature (15-25° C.). Advantageously, a temperature of between ⁇ 78° C. and ⁇ 50° C. is suitable. Then, it is desirable to allow the medium to return to ambient temperature.
  • the reaction is stoichiometric; in this case, the molar ratio of the amine (IX) to the disulfide halide (VIII) is selected at between 1 and 2, better still between 1 and 1.5.
  • the quantity used depends on the nature of the desired reaction product.
  • the amine (IX) will be in an excess in the reaction medium.
  • the molar ratio (IX)/(VIII) generally varies between 1 and 3, this ratio generally being the closest to 1, for example selected between 1 and 1.2.
  • the molar ratio of the product (VIII) to the amine (IX) will be selected to be greater than or equal to 2.
  • This molar ratio (VII)/(IX) will advantageously be between 2 and 2.3.
  • the quantity of base to be used for this reaction will be readily determined by the person skilled in the art, the base having the role of trapping the hydrohalic acid released.
  • the molar ratio of the base to the compound of formula (VIII) is greater than or equal to 1, for example between 1 and 3.
  • A, R 5 , R 6 and b are as defined above and J represents the succinimido or phthalimido group which may possibly be substituted, on the amine (IX) defined above, in the presence of a base, preferably an organic base.
  • a base preferably an organic base.
  • the substituents of the phtalimido and succinimido groups are organic substituents compatible with the reaction used, that is to say which are non-reactive under the operating conditions used.
  • the bases which are usable are those defined above for method A.
  • the reaction is carried out in an aprotic polar solvent and, preferably, an aliphatic halogenated hydrocarbon (such as methylene chloride or carbon tetrachloride) or a possibly halogenated aromatic hydrocarbon (such as a possibly halogenated benzene or a toluene).
  • the solvent is CCl 4 .
  • the reaction temperature is preferably between ⁇ 10° C. and 100° C., more preferably between 10° C. and 50° C.
  • the respective quantities of compounds (IX) and (X) used depend on the type of organosilicon compound desired, just as in the previous case (method A).
  • A, R 5 , R 6 and b are as defined above, in the presence of a base, the base preferably being as defined above.
  • the reaction temperature advantageously varies between 10 and 40° C., more preferably between 15 and 30° C., for example between 18 and 25° C.
  • reaction of compound (XII) on compound (XI) is generally carried out in a polar aprotic solvent as defined in the case of method B.
  • the solvent is benzene or toluene.
  • the reaction is a stoichiometric reaction.
  • the molar ratio of (XI) to (XII) will generally be between 1 and 1.5, better still between 1 and 1.3.
  • This variant C is in particular carried out for the preparation of the organosilicon compounds of general formula (IV) (specific formulae (V) to (VII) included) in which R 1 is other than a hydrogen atom.
  • the compounds of formula (VIII) may be prepared by reacting sulfur dichloride (SCl 2 ) on an appropriate mercaptosilane of formula (XII) as defined above, in the presence of an organic base, and preferably in the presence of triethylamine. This reaction is for example carried out in an ether at a temperature of ⁇ 78° C. to ⁇ 50° C.
  • the organic bases and the ethers are generally as defined above.
  • the amines (IX) are commercial amines, or can be easily prepared from commercial products.
  • the compounds of formula (X) are easily prepared by reacting a thiol of formula (XII) as defined above on the halide of formula: J-S-Hal (XIII) where J and Hal are as defined above.
  • This reaction is preferably carried out in the presence of a base, in particular an organic base, at a temperature of 10° C. to 50° C., for example of from 15° C. to 30° C., in particular between 18° C. and 25° C., in a polar aprotic solvent generally as defined in method B.
  • a base in particular an organic base
  • the solvent is carbon tetrachloride
  • the base is triethylamine
  • the temperature is ambient temperature.
  • This reaction is stoichiometric; nevertheless, it is desirable to operate in the presence of a deficiency of thiol (XII).
  • the molar ratio of compound (XIII) to compound (XII) is advantageously between 1 and 1.5, better still between 1 and 1.3.
  • the compounds of formula (XI) are easily obtained by reacting an amine (IX) on the halide of formula (XIII), in the presence of an organic base.
  • This reaction is preferably carried out in a solvent of halogenated hydrocarbon type (and in particular carbon tetrachloride) at a temperature generally of between 10° C. and 50° C., preferably between 15° C. and 30° C., for example between 18° C. and 25° C. (ambient temperature).
  • organic base any one of the bases defined above will be selected and, for example, triethylamine.
  • the compounds of formula (XII) are commercial compounds or can be easily prepared from commercial compounds.
  • Diagram 1 illustrates a synthesis path for the compound (XIII):
  • J and Hal are as defined above and M represents an alkali metal, preferably Na or K.
  • the commercial compound (XIV) is transformed into an alkali metal salt by the action of an appropriate inorganic base, M-OH, in which M is an alkali metal, of alkali metal hydroxide type in a C 1 -C 4 lower alcohol such as methanol or ethanol.
  • M is an alkali metal
  • alkali metal hydroxide type in a C 1 -C 4 lower alcohol such as methanol or ethanol.
  • This reaction generally takes place at a temperature of 15° C. to 25° C.
  • the resulting salt of formula (XV) is caused to react with S 2 Cl 2 to yield the compound (XVI).
  • the reaction conditions which are advantageous for this reaction are a polar aprotic solvent of the halogenated aliphatic hydrocarbon type (CH 2 Cl 2 , CCl 4 ) and a temperature of between ⁇ 20° C. and 10° C.
  • Hal-Hal on the compound (XVI) yields the expected compound (XIII).
  • operation is preferably in a polar aprotic solvent of halogenated aliphatic hydrocarbon type (such as chloroform or dichloromethane) at a temperature of between 15° C. and the reflux temperature of the solvent, preferably between 40° C. and 80° C., for example between 50° C. and 70° C.
  • Hal represents chlorine, in which case Hal-Hal is introduced into the reaction medium in gaseous form.
  • This reaction is carried out for example in an ether at a temperature of ⁇ 78° C. to ⁇ 50° C.
  • the organic bases and the ethers are generally as defined above in method A; and
  • the rubber compositions according to the invention also comprise all or same of the additives usually used in diene rubber compositions intended for the manufacture of tires, such as, for example, plasticizers, extender oils, protective agents such as anti-ozone waxes, chemical antiozonants, antioxidants, anti-fatigue agents, adhesion promoters, coupling activators such as described for example in the aforementioned applications WO00/05300 and WO00/05301, reinforcing resins such as described in WO02/10269, a cross-linking system based either on sulfur or on sulfur and/or peroxide and/or bismaleimide donors, vulcanization accelerators, vulcanization activators, etc.
  • a conventional poorly reinforcing or non-reinforcing white filler such as particles of clay, bentonite, talc, chalk or kaolin.
  • the rubber compositions according to the invention may also contain, in addition to the organosilicon compounds previously described, agents for covering the reinforcing inorganic filler, comprising for example the single Y function, or more generally processing aids liable, in known manner, owing to an improvement in the dispersion of the inorganic filler in the rubber matrix and to a reduction in the viscosity of the compositions, to improve their ability to be worked in the uncured state, these agents, being, for example, alkylalkoxysilanes, in particular alkyltriethoxysilanes, such as for example 1-octyl-triethoxysilane sold by Degussa-Hüls under the name Dynasylan Octeo, or 1-hexa-decyl-triethoxysilane sold by Degussa-Hüls under the name Si216, polyols, polyethers (for example polyethylene glycols), primary, secondary or tertiary amines (for example trialkano
  • compositions are produced in suitable mixers, using two successive preparation phases well-known to the person skilled in the art: a first phase of thermomechanical working or kneading (sometimes referred to as “non-productive” phase) at high temperature, up to a maximum temperature (T max ) of between 110° C. and 190° C., preferably between 130° C. and 180° C., followed by a second phase of mechanical working (sometimes referred to as “productive” phase) at lower temperature, typically less than 120° C., for example between 60° C.
  • T max maximum temperature
  • productive phase typically less than 120° C., for example between 60° C.
  • the manufacturing process according to the invention is characteriszed in that at least the reinforcing inorganic filler and the organosilicon compound are incorporated by kneading into the diene elastomer, during the first, so-called non-productive, phase, that is to say that at least these different base constituents are introduced into the mixer and are kneaded thermomechanically, in one or more steps, until a maximum temperature of between 110° C. and 190° C., preferably between 130° C. and 180° C., is reached.
  • the first (non-productive) phase is effected in a single thermomechanical step during which in a first phase all the base constituents necessary (diene elastomer, reinforcing inorganic filler and organosilicon compound), then in a second phase, for example after one to two minutes of kneading, any complementary covering agents or processing agents and other various additives, with the exception of the vulcanization system, are introduced into a suitable mixer, such as a conventional internal mixer.
  • a suitable mixer such as a conventional internal mixer.
  • thermomechanical working may be added in this internal mixer, after the mixture has dropped and after intermediate cooling (cooling temperature preferably less than 100° C.), with the aim of making the compositions undergo complementary thermomechanical treatment, in particular in order to improve further the dispersion, in the elastomeric matrix, of the reinforcing inorganic filler and its coupling agent.
  • the total duration of the kneading, in this non-productive phase is preferably between 2 and 10 minutes.
  • the vulcanization system is then incorporated at low temperature, generally in an external mixer such as an open mill; the entire mixture is then mixed (productive phase) for several minutes, for example between 5 and 15 minutes.
  • the final composition thus obtained is then calendered, for example in the form of a film or a sheet, or alternatively extruded, for example in order to form a rubber profiled element used for manufacturing semi-finished products such as treads, crown reinforcement plies, sidewalls, carcass reinforcement plies, beads, protectors, inner tubes or airtight internal rubbers for tubeless tires.
  • the process according to the invention for preparing an elastomeric composition usable for the manufacture of semi-finished products for tires comprises the following steps:
  • the vulcanization (or curing) is carried out in known manner at a temperature generally between 130° C. and 200° C., preferably under pressure, for a sufficient time which may vary, for example, between 5 and 90 minutes, depending, in particular, on the curing temperature, the vulcanization system adopted and the vulcanization kinetics of the composition in question.
  • the vulcanization system proper is preferably based on sulfur and a primary vulcanization accelerator, in particular an accelerator of the sulfenamide type.
  • a primary vulcanization accelerator in particular an accelerator of the sulfenamide type.
  • various known secondary accelerators or vulcanization activators such as zinc oxide, stearic acid, guanidine derivatives (in particular diphenylguanidine), etc.
  • the sulfur is used in a preferred amount of between 0.5 and 10 phr, more preferably of between 0.5 and 5.0 phr, for example between 0.5 and 3.0 phr when the invention is applied to a tire tread.
  • the primary vulcanization accelerator is used in a preferred amount of between 0.5 and 10 phr, more preferably of between 0.5 and 5.0 phr in particular when the invention applies to a tire tread.
  • the invention relates to the rubber compositions previously described, both in the “uncured” state (i.e. before curing) and in the “cured” or vulcanized state (i.e. after cross-linking or vulcanization).
  • the compositions according to the invention may be used alone or in a blend (i.e. in a mixture) with any other rubber composition usable for manufacturing tires.
  • the coupling agents usable by preference in the compositions of the invention are dithiosulfenamide silanes, more preferably alkoxysilanes corresponding to one of the formulae (V-1) to (V-3) and (VII-1) to (VII-3), synthesis methods for which are described hereafter, by way of non-limitative examples.
  • the boiling points (Eb pressure ) are given in millibars (mbar).
  • the 250 MHz proton ( 1 H-NMR) and carbon ( 13 C-NMR) spectra are recorded on a BRUCKER AC 250 spectrometer.
  • the chemical shifts ( ⁇ c and ⁇ h) are expressed in parts per million (ppm) relative to deuterochloroform (CDCl 3 ).
  • the coupling constants J are expressed in Hz.
  • the following abbreviations are used: s, singlet; bs, broad singlet; d, doublet; t, triplet; q, quartet; m, multiplet.
  • N-(3′-trimethoxysilylpropyldithio)-3-propyltriethoxysilyl-propylamine is synthesized.
  • a solution of 100 mmol (or 10.3 g) of sulfur dichloride in 400 ml of anhydrous diethyl ether is cooled to ⁇ 78° C. in a two-liter three-necked flask under an argon atmosphere. With mechanical stirring, a mixture of 3-mercaptopropyltrimethoxysilane (100 mmol) and triethylamine (100 mmol, or 10.2 g) in 150 ml of anhydrous diethyl ether is added drop by drop in one hour.
  • organoxysilane-dithiosulfenamide of formula (VII) was prepared in which:
  • N-methyl-N-(3′-triethoxysilylpropyldithio)-3′-trimethoxysilylpropylamine of formula (V-3) is synthesized in three steps.
  • the sulfide obtained in the previous step (50 mmol) is dissolved in 250 ml of benzene in a three-necked flask provided with magnetic stirring and in an inert atmosphere.
  • the 3-mercaptopropyltriethoxysilane (45 mmol) diluted in a minimum of benzene is added in one step. It is left with stirring at ambient temperature for 48 hours. The phthalimide which had precipitated and the excess sulfide were filtered off, then the solvent was evaporated at reduced pressure.
  • the procedure is as follows: the diene elastomer (or the mixture of diene elastomers, if applicable), the reinforcing filler, the coupling agent, then, after one to two minutes of kneading, the various other ingredients, with the exception of the vulcanization system, are introduced into an internal mixer filled to 70%, the initial tank temperature of which is approximately 60° C. Thermomechanical working (non-productive phase) is then performed in two stages (total duration of kneading equal to about 7 minutes), until a maximum “dropping” temperature of about 165° C. is reached. The mixture thus obtained is recovered, cooled and then the vulcanization system (sulfur and sulfenamide accelerator) is added on an external mixer (homo-finisher) at 30° C., by mixing everything (productive phase) for 3 to 10 minutes.
  • the vulcanization system sulfur and sulfenamide accelerator
  • compositions thus obtained are then calendered either in the form of thin slabs (thickness of 2 to 3 mm) or thin sheets of rubber in order to measure their physical or mechanical properties, or in the form of profiled elements usable directly, after cutting out and/or assembling to the desired dimensions, for example as semi-finished products for tires, in particular as tire treads.
  • the reinforcing inorganic filler constitutes the entire reinforcing filler, used in a preferred amount within a range from 50 to 100 phr; but it goes without saying for the person skilled in the art that a fraction of the latter, preferably a minority fraction, could be replaced by carbon black.
  • the object of this test is to demonstrate the improved (inorganic filler/diene elastomer) coupling performance in a composition according to the invention, compared with a composition of the prior art using a conventional TESPT coupling agent:
  • TESPT is bis(3-triethoxysilylpropyl)tetrasulfide, of formula [(C 2 H 5 O) 3 Si(CH 2 ) 3 S 2 ] 2 ; it is sold, for example, by Degussa under the name Si69 (or X50S when it is supported to 50% by weight on carbon black), or alternatively by Witco under the name Silquest A1289 (in both cases, a commercial mixture of polysulfides S x having an average value of x which is close to 4).
  • Table 1 gives the formulation of the two compositions (amounts of the various products expressed in phr); the vulcanization system is formed of sulfur and sulfenamide.
  • the amount of coupling agent is in both cases less than 10 phr, which represents less than 15% by weight relative to the quantity of reinforcing inorganic filler.
  • FIGS. 1 and 2 reproduce respectively the rheograms (torque in dN.m as a function of the vulcanization time in min) and, after curing (40 min at 150° C.), the curves of modulus (in MPa) as a function of elongation (in %); these curves are marked C1 and C2 in FIG. 1 , then C1′ and C2′ in FIG. 2 , and they correspond respectively to compositions C-1 and C-2.
  • the composition of the invention (curve C2), compared with the control composition (curve C1), reveals properties at break which are substantially equivalent, but a level of reinforcement (modulus) which is distinctly superior, in particular at high deformation (elongations of 100% and more), the distance between the two curves becoming all the more pronounced as the elongation increases.
  • Such behavior clearly illustrates improved coupling between the reinforcing inorganic filler and the diene elastomer, which makes it possible to predict a very good ability of the composition of the invention to resist wear.
  • the Mooney plasticity which is already low on the control composition, is unexpectedly reduced (close to 10%) on the composition of the invention (C-2), another advantage indicating an excellent ability of the compositions of the invention to be processed in the uncured state.
  • the coupling agent selected for the compositions according to the invention imparts to the latter high reinforcement properties, excellent processing properties in the uncured state and a very good ability to be vulcanized, which reveals an overall effectiveness greater than that of TESPT, which is still considered today as the (inorganic filler/elastomer) coupling agent of reference in diene rubber compositions reinforced with an inorganic filler such as a reinforcing silica.
  • the invention can be applied particularly advantageously in rubber compositions intended for the manufacture of treads for tires which have both low rolling resistance and high wear resistance, in particular when these treads are intended for tires for passenger vehicles, motorcycles or industrial vehicles of the heavy-vehicle type.

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US20060235120A1 (en) * 2002-10-31 2006-10-19 Takeaki Saiki Method for the preparation of a silicon-containing polysulfide-type polymer
US20100069568A1 (en) * 2006-12-19 2010-03-18 Dow Global Technologies Inc. Sulfide modified elastomeric polymers

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FR2886308B1 (fr) * 2005-05-26 2007-07-20 Rhodia Chimie Sa Utilisation d'un compose organosilicique fonctionnalise porteur d'au moins une fonction azo activee, comme agent de couplage(charge blanche-elastomere)dans les compositions de caoutchouc comprenant une charge inorganique
ES2332151T3 (es) * 2005-10-19 2010-01-27 Dow Global Technologies Inc. Polimeros elastomericos modificados en el extremo de la cadena con un silano-sulfuro.
WO2009104766A1 (ja) * 2008-02-22 2009-08-27 株式会社ブリヂストン 有機ケイ素化合物、並びにそれを用いたゴム組成物、タイヤ、プライマー組成物、塗料組成物及び接着剤
JP5513010B2 (ja) * 2009-05-20 2014-06-04 株式会社ブリヂストン 有機ケイ素化合物、並びにそれを用いたゴム組成物、タイヤ、プライマー組成物、塗料組成物及び接着剤
CN102395473B (zh) 2009-04-29 2014-12-17 米其林集团总公司 用于重型车辆轮胎的胎面
FR2947828B1 (fr) 2009-07-10 2012-01-06 Michelin Soc Tech Composition a base de caoutchouc naturel et d'un compose poly-imine
FR2947829B1 (fr) 2009-07-10 2012-02-24 Michelin Soc Tech Composition a base de caoutchouc naturel et d'un compose poly-amine
FR2947827B1 (fr) 2009-07-10 2012-01-06 Michelin Soc Tech Composition a base de caoutchouc naturel et d'un compose poly-imine
FR2962737B1 (fr) * 2010-07-13 2012-08-17 Michelin Soc Tech Composition de caoutchouc contenant un elastomere modifie, son procede de preparation et pneumatique la contenant
FR2986531B1 (fr) 2012-02-07 2014-02-28 Michelin & Cie Composition a base de caoutchouc naturel et d'un compose poly-aldimine
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DE60233661D1 (de) 2009-10-22
WO2003002653A1 (fr) 2003-01-09
ATE442407T1 (de) 2009-09-15
CN1522277A (zh) 2004-08-18
US20040181000A1 (en) 2004-09-16
JP4585762B2 (ja) 2010-11-24
CN1277873C (zh) 2006-10-04
EP1409581B1 (de) 2009-09-09
JP2004533522A (ja) 2004-11-04

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